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EP1593705B1 - Utilisation des acides phosphoniques ou phosphiniques organiques, ou des oxides, hydroxides ou des sels des acides carboxyliques comme stabilisateurs de chaleur pour des polyhydroxyalcanoates - Google Patents

Utilisation des acides phosphoniques ou phosphiniques organiques, ou des oxides, hydroxides ou des sels des acides carboxyliques comme stabilisateurs de chaleur pour des polyhydroxyalcanoates Download PDF

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Publication number
EP1593705B1
EP1593705B1 EP05076115A EP05076115A EP1593705B1 EP 1593705 B1 EP1593705 B1 EP 1593705B1 EP 05076115 A EP05076115 A EP 05076115A EP 05076115 A EP05076115 A EP 05076115A EP 1593705 B1 EP1593705 B1 EP 1593705B1
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EP
European Patent Office
Prior art keywords
pha
acid
poly
compound
adipic acid
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EP05076115A
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German (de)
English (en)
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EP1593705A1 (fr
Inventor
Jawed Asrar
Jean R. Pierre
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Yield10 Bioscience Inc
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Metabolix Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention relates generally to the thermal stabilisation of biodegradable polyester compositions and in particular of high molecular weight polyhydroxyalkanoates (PHAs) containing one or more plasticizers. It also relates to the use of such compositions in the production of PHA shaped objects/articles.
  • PHAs high molecular weight polyhydroxyalkanoates
  • biodegradable polymers There has been considerable interest in recent years in the use of biodegradable polymers to address concerns over plastic waste accumulation.
  • the potential worldwide market for biodegradable polymers is enormous (> 10 B lbs/yr).
  • Some of the markets and applications most amenable to the use of such biopolymers involve those having single, short use applications, including packaging, personal hygiene, garbage bags, and others. These applications, although poorly suited for recycling, are ideally suited for biodegradation through composting.
  • PHA biopolymers are polyesters produced by numerous microorganisms in response to nutrient limitation.
  • the commercial potential for PHA spans many industries, and is derived primarily from certain advantageous properties which distinguish PHA polymers from petrochemical-derived polymers and other polymers derived from renewable resources, namely excellent biodegradability and/or natural renewability compared to the petrochemical-derived polymers, and hydrophobicity compared to other polymers derived from renewable resources.
  • PHA is one of the most thermosensitive of all commercially available polymers. As such, a dramatic rate of polymer degradation is observed at the temperatures typically required for conventional processing of PHA into end-products such as films, coatings, fibers etc.
  • An additional limitation of the potential utility of PHA polymers relates to the observation that certain characteristics such as ductility, flexibility and elongation of the polymer diminish over time. This rapid "aging" of certain PHA-derived products is unacceptable their intended useful life.
  • the success of PHA as a viable alternative to both petrochemical-derived polymers and to non-PHA biodegradable polymers, will depend upon novel approaches to overcome the unique difficulties associated with PHA polymer processing and with products derived therefrom.
  • Polymeric films with properties suitable for diverse applications have been difficult to prepare using PHAs due to their frequently unacceptable mechanical characteristics, for example poor melt strength, rapid aging, and brittleness.
  • GB 2,243,327 teaches that biodegradable PHA polymers, such as polyhydroxybutyrate-co-valerate (PHBV) copolymer, cannot be formed into thin films while maintaining the required strength and tear resistance for applications such as a diaper backsheet.
  • PHBV polyhydroxybutyrate-co-valerate
  • This problem was addressed by combining a thin biodegradable thermoplastic polymer film into a sheet laminate with at least one layer of a fiber substrate comprised of biodegradable fibers.
  • PHBV polyhydroxybutyrate-co-valerate
  • U.S. Patent No. 4,880,592 discloses a means of achieving a free-standing PHBV film for diaper backsheet applications by coextruding the PHBV between two layers of sacrificial polymer, for example polyolefins, stretching and orienting the multilayer film, and then stripping away the polyolefin layers after the PHBV has had time to crystallize.
  • the PHBV film is then laminated to either water soluble films or water insoluble films such as PVDC or other polyolefins.
  • WO 94/00293 discloses multilayer films wherein the PHBV component may be coextruded as an internal layer surrounded by outer layers of films (e.g. biodegradable films) to be used in the application (e.g. diaper films) so that the external layers are not stripped away from the PHBV layer. They remain as an integral part of a biodegradable multilayer film.
  • films e.g. biodegradable films
  • EP 736,563 describes a process for producing cast and blown films from PHBV copolymers that have been compounded with plasticizers, nucleating agents and/or other additives. No specifications of the copolymer were disclosed other than an HV content of 4-16%.
  • the molecular weights of the PHBV powder used in the examples ranged up to 520,000 before compounding and extrusion into pellets.
  • films of the compounded PHBV were extruded on a preformed supportive bubble of EVA-resin or LDPE with MFI less than 2.5 g/10min.
  • WO 94/28061 describes granules of PHA plasticized with polyester adipates.
  • US 56 46 217 describes granules of PHA comprising a transesterification catalyst and a plasticizer.
  • the present invention describes the use of certain compounds as thermal stabilizers in pellet compositions comprising PHA, wherein the Mw of the PHA in the pellets is preferably greater than 470,000.
  • the pellets are normally produced by melting PHA powder having a Mw greater than 500,000, extruding a strand of the melted PHA, cooling and crystallizing the extruded strand and cutting the strands into pellets.
  • the pellets so produced are suitable for use in the production of numerous PHA end products by extrusion, molding, coating, spinning and calendaring operations, in particular extrusion blow molded and stretch blow molded containers and bottles, calendered and thermoformed sheets and general extruded parts.
  • the pellet compositions are particularly useful in the production of blown and cast free-standing films as described herein.
  • the PHA pellet compositions include one or more polyester plasticizers in accordance with claim 1.
  • the thermal stabilizers comprise compounds having the following general structure: where R' is R or OH, and R is a branched or unbranched saturated C 1 -C 30 group, a branched or unbranched unsaturated C 2 -C 30 group, a C 6 -C 30 aromatic group, or a saturated or unsaturated C 6 -C 30 cycloaliphatic group.
  • the compounds may contain one or more O, N or S atoms in the alkyl chains and may optionally be substituted with one or more groups selected from hydroxyl, halo, carboxylic acid or ester, cyano, aryl, amino, hydroxylamino, mono-, di-, or trialkyl amino or phosphonic acid.
  • thermal stabilizers of this class of phosphorous-containing compounds include cyclohexylphosphonic acid, 1-cyclohexenylphosphonic acid, 1-hydroxycyclohexenylphosphonic acid, 1-hexanephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, dicyclohexylphosponic acid and 2,4,4-(trimethylpentyl)cyclohexylphosphonic acid.
  • the thermal stabilizer can also comprise oxides, hydroxides, and saturated or unsaturated carboxylic acid salts of a metals from Groups I to V of the Periodic Table.
  • a metals from Groups I to V of the Periodic Table For example, calcium stearate, barium stearate, magnesium stearate, zinc stearate, and zinc oxide are particularly suitable for use as PHA thermal stabilizers according to the present invention.
  • the thermal stabilizer may comprise one of the disclosed compounds or may comprise a mixture thereof.
  • pellet compositions suitable for producing PHA films can have a PHA Mw as low as about 435,000, while still maintaining the ability to produce film having the desired Mw of greater than 420,000.
  • the Mw of the PHA powder can be as low as about 480,000.
  • the thermally stabilized PHA compositions are useful for the production of polymeric objects for numerous applications.
  • the objects can be produced, for example, by extrusion, molding, coating, spinning and calendaring operations, in particular extrusion blow molded and stretch blow molded containers and bottles, cast and extruded films, calendered and thermoformed sheets, general extruded parts, solution and melt spun fibers, and foamed materials and products.
  • PHAs are biodegradable polymers or copolymers having the following general structure for one or more of the repeating units: where a is 0 to 6, b is 0 to 15, Y is H, F, Cl, Br, CN, OH, CO 2 H, CO 2 R (where R is alkyl, benzyl etc.), methyl, cyclohexyl, phenyl, p-nitrophenoxy, p-cyanophenoxy, phenoxy, acetoxy, vinyl, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, etc., and n is an integer typically between 10 and 25,000.
  • the pendant groups of the repeating units may contain additional functionalization such as double bonds, epoxidized double bonds, hydroxyl groups, alkyl groups, alkenyl groups etc. or combinations thereof.
  • the polymer main chain can contain up to 8 carbons in the repeating units and there may be additional functionalization in or on the main chain such as double bonds, alkyl groups, alkenyl groups, hydroxyl groups etc. or combinations thereof.
  • the PHA is preferably one capable of being biologically produced, for example in a plant or microbial organism. Most typically, it is a fermentation product, particularly of a microbiological process, whereby a microorganism lays down polyhydroxyalkanoate during normal or manipulated growth. Manipulation may be achieved by removing or failing to produce one or more nutrients necessary for cell multiplication. Numerous microbiological species are known in the art to be suitable for the production of polyhydroxyalkanoate polymers (see for example, Anderson and Dawe Micro. Rev. 54 (4): 450-472, 1990 ). The microorganisms may be wild type or mutated or may have the necessary genetic material introduced into it, for example by any of the methods or recombinant DNA technology. It is to be emphasized that it is not necessary for the PHA- producing organism to be a microorganism, but at present such organisms are preferred.
  • the PHAs preferably have as constituents hydroxyalkanoates (HA) monomers which are substrates for PHA synthase enzymes.
  • HA hydroxyalkanoates
  • Biologically-produced PHA polymers are the product of PHA synthase microbial enzymes, and are produced in either a bacterial cell which naturally contains a PHA synthase, or in a bacterial or other cell type, for example a plant cell, which has been genetically engineered to express such an enzyme.
  • the microbial PHA synthase enzymes have broad substrate ranges and are capable of incorporating a large number of HA monomers as constituents of biosynthetic PHA depending upon growth conditions, precursor substrate availability, and the source of the PHA synthase enzyme.
  • Suitable HA monomers can include those having the following formula: where a is 0 to 6, b is 0 to 15 and Y is H, F, Cl, Br, CN, OH, CO 2 H, CO 2 R (where R is alkyl, benzyl etc.), methyl, cyclohexyl, phenyl, p-nitrophenoxy, p-cyanophenoxy, phenoxy, acetoxy, vinyl, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, etc. As in the above description, there may be additional functionalization in or on the pendant and/or main chains.
  • the monomers can be homopolymerized or copolymerized either biochemically or synthetically to produce the polymer.
  • the polymer can also be a blend of two or more PHAs differing in the value of m.
  • a particular example contains:
  • the polymer is a poly (hydroxybutyrate/valerate) copolymer or blend of copolymers.
  • compositions of the invention may contain a blend of biodegradable polyesters.
  • Blends of particular interest are blends of PHA with polycaprolactone, polylactic acid, and cellulose esters and up to 50 % w/w of the blend preferably comprises one or more polymers selected from polycaprolactone, polylactic acid, and cellulose esters.
  • molecular weight refers to the weight average molecular weight (Mw) as opposed to the number average molecular weight (Mn).
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw and Mn The most commonly used technique for determining Mw and Mn is by gel permeation chromatography (GPC). This method is capable of determining the entire molecular weight distribution of a polymer sample from which molecular weight averages can be determined.
  • GPC gel permeation chromatography
  • Other methods known in the art for determining Mw and Mn include osmometry, scattering and sedimentation (See for example, W. R. Sorensen & T. W. Campbell: Preparative Methods of Polymer Chemistry, Interscience Publishers, NY, 1961 ).
  • pellets For most processes that produce thermoplastic polymer products such as films and molded articles, it is desirable to have a polymer, polymer blend or polymer formulation supplied to the processor in the form of pellets. This allows the polymeric material to be provided to the processor preformulated for a particular application.
  • the use of pellets are advantageous in that they avoid problems with dust typically encountered when handling powders.
  • such pellets are prepared by melt extruding continuous strands of a polymer, polymer blend or the polymer formulation and then cutting the strands into pellets of a desired length.
  • pellets containing PHA of molecular weights greater than 470,000 are extremely useful in the production of PHA films having desirable characteristics not previously observed. For example, due to the low melt strength of PHA, blown PHA films have not been successfully produced without employing the use of a supporting film.
  • the pellet compositions stabilized according to this invention allow for the production of blown and cast free-standing PHA films having excellent properties while not requiring use of a supporting film.
  • the PHA pellet compositions have a desirably low melt flow index (MFI) less than 20, preferably less than 14, and more preferably less than 8 g/ 10min (170° C/5 kg load).
  • pellets are also useful in the production of other PHA end products by extrusion, molding, coating, spinning and calendaring operations, in particular extrusion blow molded and stretch blow molded containers and bottles, calendered and thermoformed sheets, general extruded parts, solution and melt spun fibers and foamed materials and products.
  • PHA pellets having high molecular weights have been difficult to produce due to the thermosensitivity of PHA at the processing conditions typically used in the art for pellet production. It is well known in the art that high temperatures produce very rapid PHA degradation. (See for example, Grassie, N., Murray, E. J. and Holmes, P.A.-Polym. Degrad. Stab. 6, pp. 47,95,127 (1984 )).
  • the processing conditions disclosed herein serve to minimize the thermal degradation of PHA during processing into pellets. Factors which can effect such degradation include the temperature at which extrusion is performed, the time of exposure to such temperatures, screw speed, shear heating, and screw and die design.
  • the pellets are generally produced by extrusion of PHA powder under conditions of low shear and temperature control, either in a single or twin screw extruder.
  • the present method allows for the production of high molecular weight PHA pellets without excessively compromising the stability of the polymer in response to the conditions required for their production.
  • the molecular weight of the PHA in the pellet compositions is determined in part by the molecular weight of the PHA powder used as the starting material to make the pellets.
  • the PHA in the powder used to produce the PHA-containing pellets typically has a Mw greater than 500,000.
  • the PHA pellets contain one or more plasticizers.
  • Plasticizers for use in the PHA pellet compositions are known to the skilled individual in this art, particularly those described in WO 94/28061 . Such plasticizers are well suited for applications where improved impact strength and/or ductility are important.
  • the plasticizer is a material capable of plasticizing PHA, i.e. capable of improving the ductility of the polyester and especially a material capable of plasticizing PHB or PHBV.
  • the range up to 40 phr w/w includes most of the likely uses and, for making effectively rigid but not brittle articles, the range 5-25 phr w/w is generally suitable.
  • the composition may contain one or more plasticizers selected from those defined herein and may additionally contain one or more plasticizers previously known to plasticize polyhydroxyalkanoates, for example, citrates containing doubly esterified hydroxycarboxylic acids having at least 3 ester groups in the molecule, glycerol triacetate and glycerol diacetate.
  • compositions can additionally contain the usual polymer processing additives such as fillers, fibers, nucleants, and pigments such as titanium dioxide. It can be in the form of moldings, extrudates, coatings, films or fibers, including multilayer coatings, films or fibers. Because many of the above plasticizers provide improved elongational properties that can be better sustained over time than the properties of non-plasticized materials, intermediate forms of the plasticized compositions, such as sheets and films, are advantageous since they would retain sufficient properties for forming into final products over a period of several months.
  • polymer processing additives such as fillers, fibers, nucleants, and pigments such as titanium dioxide. It can be in the form of moldings, extrudates, coatings, films or fibers, including multilayer coatings, films or fibers. Because many of the above plasticizers provide improved elongational properties that can be better sustained over time than the properties of non-plasticized materials, intermediate forms of the plasticized compositions, such as sheets and films, are advantageous since they would retain sufficient properties for
  • Nucleants are also typically used in producing the PHA pellets. Suitable nucleants can be selected from those known in the art, for example particulate nucleants such as saccharin, talc, boron nitride, ammonium chloride, PHB seed crystals, "polymer soluble” nucleants such as organic phosphonic acids and their combinations with stearic acid salts (see for example WO 91/19759 ).
  • particulate nucleants such as saccharin, talc, boron nitride, ammonium chloride, PHB seed crystals
  • polymer soluble nucleants such as organic phosphonic acids and their combinations with stearic acid salts (see for example WO 91/19759 ).
  • a preferred nucleant is one having the following structure: where R can be hydroxy, hydrogen, C1-C25 alkyl groups (with or without one or more substituent groups such as -OH, - CO2H, -Cl, -Br, -NH2, -N(alkyl)H or N(alkyl)2), cycloalkyl groups, aryl or arylalkyl groups (such as phenyl, benzyl, etc. with or without substituents on the aromatic rings).
  • R can be hydroxy, hydrogen, C1-C25 alkyl groups (with or without one or more substituent groups such as -OH, - CO2H, -Cl, -Br, -NH2, -N(alkyl)H or N(alkyl)2), cycloalkyl groups, aryl or arylalkyl groups (such as phenyl, benzyl, etc. with or without substituents on the aromatic rings).
  • Synthesis of such compounds
  • the synthesis can also be applied to dibasic acids such as adipic acid, succinic acid, etc. to give the corresponding tetrakis phosphonic acid (i.e., di-ODPAs) which can also be used as nucleants.
  • di-ODPAs tetrakis phosphonic acid
  • 1,6-dihydroxy-1,6-dihexanediylidene tetraphosphonic acid is obtained (Aus. 599950 ).
  • methylene diphosphonic acid PL 131549
  • carbonyl diphosphonic acid CA 93:182031
  • ODPAs organodiphosphonic acids
  • the ODPA or di-ODPA may also be formed in situ, for example by reaction of the corresponding phosphinic acid.
  • Preferred ODPAs include 1-hydroxy-lower alkylidene-1,1-diphosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1-hydroxypropylidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-phosphonic acid, 1-hydroxycyclohexylidene-1,1-diphosphonic acid.
  • HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
  • both acid moieties are phosphonic acid moieties
  • R1 is a methyl group
  • R2 is hydroxy group (i.e., HEDP).
  • HEDP is available as a mixture of HEDP in water from Monsanto Company (800 N. Lindbergh, St.
  • the ODPA is used in amounts typically in the range of 0.01 - 5.0 phr (parts per hundred resin), more preferably about 0.02 - 1.0 phr, most preferably 0.02 - 0.5 phr.
  • the nucleants can further be metallic salts of ODPAs, preferably mono-metallic salts. However, it is generally preferred that not all, e.g., less than 70%, more preferably less than 60% of the phosphonic acid moieties are involved in the salt formation since it has been found that excessive salt formation may adversely influence the effectiveness of certain nucleants.
  • Organic metal salts and/or certain inorganic compounds can be used to further improve nucleation activity and/or reduce the extent of discoloration and/or improve the clarity of PHA-derived products when used in combination with the ODPAs of the invention.
  • the organic metal salt is preferably an organic acid salt, more preferably a fatty acid metal salt.
  • the inorganic compound is preferably an metal oxide, a metal hydroxide or a metal carbonate. Suitable metals include those selected from Groups I to V of the periodic table, preferably aluminum, antimony, tin, sodium, calcium, magnesium, barium or zinc. Most preferably the metal is one which has benign environmental and toxicological properties such as magnesium, calcium and barium.
  • Preferred fatty acids include stearic acid, palmitic acid, acetic acid, propionic acid, caproic acid, oleic acid, behenic acid and montanic acid.
  • the fatty acid metal salt of the invention is calcium stearate or magnesium stearate which have proven highly effective in combination with ODPAs in nucleating thermoplastic polyesters.
  • the organic metal salt or the inorganic metal oxide, metal hydroxide or metal carbonate is used in an amount typically ranging from 0.001 to 5 phr (parts per hundred of resin), preferably about 0.005 to 2 phr, and most preferably about 0.01 to 0.5 phr.
  • a nucleant formulation preferably comprises organic metal salt (or inorganic metal oxide, metal hydroxide or metal carbonate) and ODPA in weight ratios of about 0.01:1 1 to 10:1, preferably about 0.05:1 to 7.5:1, and more preferably about 0.1:1 to 5:1.
  • organic metal salt or inorganic metal oxide, metal hydroxide or metal carbonate
  • ODPA in weight ratios of about 0.01:1 1 to 10:1, preferably about 0.05:1 to 7.5:1, and more preferably about 0.1:1 to 5:1.
  • the weak organic base is one which is effective in improving the elongational properties and/or clarity of the polymeric material.
  • the weak organic base should be polymer-miscible or -soluble and melt at a sufficiently high temperature so that, if desired, nucleating agent solvent can be readily removed during preparation.
  • the weak organic base preferably comprises a mono-, bis-, or tri- fatty acid amide, as these generally exhibit good hydrolytic stability in the presence of ODPAs. More preferably, the weak organic base is a stearamide, for example ethylene bistearamide (EBS), available from Lonza or Henkel under the tradename Acrawax C or Loxamid EBS.
  • EBS ethylene bistearamide
  • the weak organic base is typically present in the polymeric compositions in an amount between about 0.01 to 9.0 phr, preferably between about 0.05 to 1.0 phr, most preferably about 0.1 to 0.5 phr.
  • One nucleant system that can be used comprises phosphonate/calcium stearate/EBS present in ratios effective for nucleating PHA and producing PHA articles having excellent clarity, color, elongational and tensile properties.
  • This system is soluble in the polymer and also stabilizes PHA against thermal degradation.
  • the phosphonates that can be used include those described as phosphorous-containing compounds under "PHA Thermal Stabilization" below.
  • This nucleant system is especially suitable for nucleating PHBV to obtain a clear composition for use as a film.
  • a most preferred nucleant for use in this invention comprises HEDP/calcium stearate/EBS present in ratios effective for nucleating PHA and producing PHA articles having excellent clarity, color, elongational and tensile properties. Most preferably, the constituents of this formulation are present in weight ratios of about 0.8/1.5/1.7 respectively.
  • Suitable levels of such a nucleant formulation to be added to the PHA range from about 0.01 to 5.0 parts per hundred of resin (phr).
  • the level of the nucleant formulation is about 0.05 - 1.0 phr, and most preferably it is about 0.1 - 0.6 phr.
  • the solvent is then removed, for example by evaporation under vacuum, giving rise to solids which are ground, pulverized, or otherwise treated so as to produce particles with diameters less than about 710 microns, preferably less than about 350 microns.
  • effective nucleating agent solvent herein means a solvent which dissolves the ODPA and preferably enhances its nucleation activity but which does not intolerably reduce its effectiveness as a nucleant.
  • the ODPA prepared using an effective nucleating agent solvent as described herein will have at least as effective nucleation activity, preferably greater nucleation activity, compared to the same ODPA that is not dissolved in an effective nucleating agent solvent during its preparation or use.
  • Nucleating agent solvents for use in this invention include but are not limited to C I to C6 aliphatic mono, di- and tri- ols such as methanol, ethanol, ethylene glycol, 1- or 2-propanol, propylene glycol, glycerol, 2-methyl-2-propanol, 2-butanol and the like, and further including mixtures of such solvents with each other and with water.
  • Preferred nucleating agent solvents include methanol, ethanol or another lower alcohols, or mixtures of such alcohols with water to allow for easy solvent removal.
  • the nucleating agent solvent needs to be appropriately selected since it has been found that some solvents such as acetone and tetrahydrofuran when used with some ODPAs such as HEDP are not effective nucleating agent solvents.
  • mixtures of solvents e.g. methanol and acetone, can serve as effective nucleating agent solvents as defined herein even though one of the solvents in the mixture is not an effective nucleating agent solvent when used alone. While all of the solvents which will be effective nucleating agent solvents has not yet been elucidated, a person skilled in the art can readily determine whether a proposed solvent for an ODPA is "effective" by routine experimentation following the description herein.
  • the PHA pellet compositions may include a number of additives or other components which are commonly included in polymeric materials.
  • These may include, for example, dyes, fillers, stabilizers, modifiers, anti-blocking additives, antistatic agents etc.
  • thermal stabilizers can reduce the extent of molecular weight loss due to PHA degradation normally observed during compounding of PHA powder into PHA pellets, and during processing of PHA pellets into end products such as films.
  • the present method is applicable to any situation where it is desirable to minimize PHA degradation during exposure to temperatures or other conditions which would typically cause such degradation.
  • Thermal degradation of PHA is generally believed to take place by chain scission involving the formation of a six-membered transition state. Unlike most polymers, where thermal degradation is a free radical process, it has been reported and generally accepted that free radical scavengers and known thermal stabilizers have not been effective in stabilizing PHA against thermal degradation.
  • thermal stabilizers of the present invention comprise compounds having the following structural formula: where R' is R or OH, and R is a branched or unbranched saturated C 1 -C 30 group, a branched or unbranched unsaturated C 2 -C 30 group, a C 6 -C 30 aromatic group, or a saturated or unsaturated C 6 -C 30 cycloaliphatic group.
  • the compounds may contain one or more O, N or S atoms in the alkyl chains and may optionally be substituted with one or more groups selected from but not limited to hydroxyl, halo, carboxylic acid or ester, cyano, aryl, amino, hydroxylamino, mono-, di-, or trialkyl amino, phosphonic acid, etc.
  • thermal stabilizers of this class of phosphorous-containing compounds include cyclohexylphosphonic acid (DZB), 1-cyclohexenylphosphonic acid, 1-hydroxycyclohexenylphosphonic acid, 1-hexanephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, or dicyclohexylphosponic acid, 2,4,4-(trimethylpentyl)cyclohexylphosphonic acid. Particularly useful are cyclohexylphosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid.
  • thermo-oxidative degradation may also be operative in reducing the Mw of PHA during thermal processing since phosphorous-containing compounds can act as oxygen scavengers.
  • Metal compounds suitable for use in the present invention include oxides, hydroxides, and saturated or unsaturated carboxylic acid salts of metals from Groups I to V of the Periodic Table. These can include, for example, compounds of aluminum, antimony, barium, tin, sodium, calcium, magnesium and zinc.
  • the carboxylic acids can include stearates and palmitates. Particularly useful are fatty acid salts such as calcium stearate (CaSt), magnesium stearate (MgSt), zinc stearate (ZnSt), and zinc oxide.
  • a single thermal stabilizer may be used in an amount sufficient to inhibit PHA degradation.
  • a combination of thermal stabilizers can be used.
  • both DZB and zinc stearate are dry blended with the PHA powder used to produce PHA pellets.
  • a DZB/ZnSt combination has been used as a nucleant system in some settings (see for example WO 91/19759 ) the ability of such compounds to act as thermal stabilizers for PHA has not been previously recognized. This invention demonstrates that the presence of DZB and ZnSt results in significantly less PHA degradation during the pellet forming process.
  • PHA pellets extruded with DZB and ZnSt show significantly less molecular weight loss relative to the PHA powder used to produce them than PHA pellets extruded with the commonly used nucleant, boron nitride. Furthermore, when these pellets are melt processed into films, significantly less Mw reduction during film production is observed, as further described below.
  • the stabilized pellets are especially useful for making shaped articles such as films, especially for packaging, fibers, non-woven fabrics, extruded nets, personal hygiene products, bottles and drinking vessels, agricultural and horticultural films and vessels, ostomy bags, coated products (such as paper, paperboard, non-woven fabrics), agricultural and horticultural films and vessels, slow-release devices.
  • the polymer composition with suitable additives can be used as an adhesive.
  • Extruded PHAs having molecular weights greater than 420,000 provide a desirable combination of melt strength during initial film formation and subsequent drawability sufficient for use in stable blown film and cast film processes.
  • the PHA films are preferably oriented, either mono- or bi-axially, in order to maximize mechanical properties.
  • Bi-axially oriented means to stretch the film along a direction in which it travels, called the machine direction, and in a direction 90° to the machine direction in the plane of the film, known as the transverse direction, thereby extending length and width of the film to greater than its initial dimensions.
  • Bi-axial orientation may involve simultaneous or sequential stretching.
  • Mono-axial orientation refers to stretching in either the machine direction or the transverse direction, but not both.
  • PHA film compositions of the present invention are formed into films of a uniform thickness ranging from about 75 to 150 microns prior to orientation, and ranging from about 5 to 100 microns after orientation.
  • Films typically exhibit elongation to break greater than 65%, preferably greater than 75%, and more preferably greater than 100%.
  • the tensile strength of the films is typically greater than 50 MPa, preferably greater than 75 MPa, and more preferably greater than 90 MPa.
  • the presence of DZB and ZnSt in the pellets used to produce the films resulted in only a 3% PHA Mw loss during film processing compared to 14.1 % when boron nitride was used as a nucleant (see Example 21).
  • the molecular weight of the PHA in the pellet can be as low as 435,000 while still allowing for the production of blown film containing PHA of the desired molecular weight greater than 420,000.
  • the PHA film compositions may include a number of additives or other components which are commonly included in polymeric films.
  • These may include, for example, dyes, fillers, stabilizers, modifiers, anti-blocking additives, antistatic agents etc.
  • the PHA films are useful for numerous applications involving packaging, bags and/or membranes.
  • the films are particularly well suited for production of food and non-food packaging, protecting films, trash bags, blisters, slit film woven bags, composting bags, shopping bags and bubble films.
  • Low melt strength creates a need to operate cast film lines at slow line speeds or to use a supporting film or web onto which the PHBV is cast and later isolated as a free-standing film by peeling away the supporting film.
  • Low melt strength makes it extremely difficult to produce blown film without the use of a supporting blown film.
  • residual tack of the PHA can cause the tubular film to stick to itself after it has been cooled and collapsed for winding.
  • the method involves melt processing PHA, preferably in the form of the PHA pellets of this invention, forming the melt into a film, for example by blowing a bubble through a circular die or by casting on cooling rolls through a T shape flat die, and orienting the film by continuous mono- or bi-axial stretching.
  • the Mw of the PHA in the film is greater than 420,000.
  • the Mw of the PHA in the pellets used to produce the film can be as low as 435,000 while still being suitable for producing film containing PHA of the desired Mw greater than 420,000.
  • the films can be formed by a variety of known techniques, such as extrusion processes including calendering, flat die extrusion and film blowing, in addition to casting solutions or suspensions of polymeric compositions followed by solvent recovery.
  • the molecular weight of the PHA in the pellets is critical in achieving a stable film blowing process in accordance with this method.
  • PHA pellets having molecular weights less than 435,000 are not suitable for the production of blown films due in part to bubble instability caused by low melt strength.
  • Film blowing processes are well known in the art (see for example Rosato & Rosato, Plasticizer Processing Data Handbook . Van Nostrand Reinhold (Pub.), NY, 1990). Film blowing typically involves melt extrusion of a tubular preform, cooling the preform, blowing the preform with air such that a stable bubble is formed, collapsing the bubble between nip rolls to produce a film. During blown film processing, the blow up ratio determines the amount of circumferential orientation and the pull rate of the bubble determines longitudinal orientation. With PHA films, mono orientation can be achieved by operating with a puller roll speed to feeder roll speed sufficient to give a draw ratio in the 2-6 range. The cooling rate (air flow), thickness, diameter and height of the bubble are adjusted so that the PHA tubular film is sufficiently crystalline to produce orientation and prevent sticking and blocking, but not too crystalline so as to exhibit undesirable stiffness and brittleness which would prevent the continuous drawing operation.
  • a tentering frame In orienting film or sheet, a tentering frame may be used which has continuous speed control and diverging tracks with holding clamps. As the clamps move apart at prescribed diverging angles, the hot plastic is stretched in the transverse direction resulting in monodirectional orientation. To obtain bidirectional orientation, an in-line series of heat controlled rolls are located between the extruder and tenter frame. The rotation of each succeeding roller can be increased depending upon the longitudinal stretched properties desired.

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Claims (12)

  1. Utilisation d'un composé choisi parmi :
    (a) un composé ayant la formule structurelle :
    Figure imgb0010
     dans laquelle R' est R ou OH, et R est un groupe en C1 à C30 saturé, ramifié ou non ramifié, un groupe en C2 à C30 insaturé, ramifié ou non ramifié, un groupe aromatique en C6 à C30 ou un groupe cycloaliphatique en C6 à C30 saturé ou insaturé ; ou
    (b) des oxydes, hydroxydes et sels d'acide carboxylique insaturé de métaux des groupes I à V du tableau périodique ;
    en tant que stabilisateur thermique de polyhydroxyalcanoate (PHA) en incluant le composé dans une composition contenant du PHA pour former une pastille afin d'inhiber la dégradation de PHA pendant une exposition de la composition à des températures qui entraînent une dégradation du PHA, dans laquelle la composition comprenant du PHA comprend un composé plastifiant choisi parmi le poly(1,3-butylène glycol-co-1,2-acide 1,2-propylène glycol adipique) terminé par du 2-éthylhexanol ; le poly(néopentyl glycol-co-acide 1,4-butylène glycol adipique) terminé par du 2-éthylhexanol ; le poly(acide 1,3-butylène glycol adipique) non terminé ; le poly(acide 1,3-butylène glycol adipique) non terminé ; le poly(acide 1,2-propylène glycol adipique-co-acide phtalique) terminé par du 2-éthylhexanol ; le poly(acide néopentyl glycol adipique) terminé par du 2-éthylhexanol ; le poly(1,2-propylène glycol-co-acide 1,4-butylène glycol adipique) terminé par du 2-éthylhexanol ; le poly (acide 1,3-butylène glycol adipique) terminé par des acides gras mixtes ; le poly(acide 1,2-propylène glycol adipique) terminé par du 2-éthylhexanol ; le poly(1,2-propylène glycol-co-acide 1,4-butylène glycol adipique) terminé par du 2-éthylhexanol ; le poly(acide 1,4-butylène glycol adipique) et le poly(1,4-butylène glycol-co-acide éthylène glycol adipique).
  2. Utilisation selon la revendication 1, dans laquelle le composé défini par la partie (a) de la revendication 1 contient un ou plusieurs atomes O, N ou S dans la chaîne alkyle.
  3. Utilisation selon la revendication 1 ou 2, dans laquelle le composé défini par la partie (a) de la revendication 1 est substitué par un ou plusieurs groupes choisis parmi un groupe hydroxyle, halogéno, acide carboxylique ou ester, cyano, aryle, amino, hydroxylamino, mono-, di- ou trialkyl amino ou acide phosphonique.
  4. Utilisation selon la revendication 1, dans laquelle le composé défini par la partie (a) de la revendication 1 est l'acide cyclohexylphosphonique, l'acide 1-cyclohexénylphosphonique, l'acide 1-hydroxycyclohexénylphosphonique, l'acide 1-hexanephosphonique, l'acide 1-hydroxyéthylidène-1,1-diphosphonique, l'acide dicyclohexylphosphonique ou l'acide 2,4,4-(triméthylpentyl)cyclohexylphosphonique.
  5. Utilisation selon la revendication 1, dans laquelle le composé défini par la partie (b) de la revendication 1 est un composé d'aluminium, d'antimoine, de baryum, d'étain, de sodium, de calcium, de magnésium ou de zinc.
  6. Utilisation selon la revendication 1 ou 5, dans laquelle le composé tel que défini par la partie (b) de la revendication 1 est un stéarate ou un palmitate.
  7. Utilisation selon la revendication 1, 5 ou 6, dans laquelle le composé défini par la partie (b) de la revendication 1 est le stéarate de calcium, le stéarate de magnésium, le stéarate de zinc ou l'oxyde de zinc.
  8. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le composé est utilisé comme premier stabilisateur thermique en combinaison avec un second stabilisateur thermique, le second stabilisateur thermique étant également un composé tel que défini par la revendication 1.
  9. Utilisation selon la revendication 8, dans laquelle le composé utilisé comme premier stabilisateur thermique est le stéarate de zinc, et le second stabilisateur est l'acide cyclohexylphosphonique.
  10. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le PHA dans la composition de pastille de polyester a une masse moléculaire moyenne en masse d'au moins 435 000.
  11. Utilisation selon l'une quelconque des revendications précédentes, pour inhiber la dégradation de PHA pendant la production d'un objet polymère façonné comprenant la fusion de la composition et la production d'un objet façonné à partir de celle-ci par des opérations d'extrusion, de moulage, de revêtement, de filage ou de calandrage.
  12. Utilisation selon la revendication 11, dans laquelle l'objet façonné est un film soufflé comprenant du PHA ayant une masse moléculaire en masse d'au moins 420 000.
EP05076115A 1997-10-31 1998-10-27 Utilisation des acides phosphoniques ou phosphiniques organiques, ou des oxides, hydroxides ou des sels des acides carboxyliques comme stabilisateurs de chaleur pour des polyhydroxyalcanoates Expired - Lifetime EP1593705B1 (fr)

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WO1999023146A1 (fr) 1999-05-14
AU1281499A (en) 1999-05-24
EP2050785A1 (fr) 2009-04-22
DE69841061D1 (de) 2009-09-24
EP1025152A1 (fr) 2000-08-09
ES2356354T3 (es) 2011-04-07
EP1593705A1 (fr) 2005-11-09
US6127512A (en) 2000-10-03

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